Thermodynamics of methane adsorption on copper HKUST-1 at low pressure
Abstract
Metal–organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH₄ adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH₄–CH₄ intermolecular interactions are minimized and the energetics solely reflects the CH₄–MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH₄ independent of coverage. The calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH₄ adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH₄–HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.
- Authors:
-
- Univ. of California, Davis, CA (United States)
- Univ. of California, Davis, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- East China Univ. of Science and Technology, Shanghai (China)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1221609
- Report Number(s):
- LA-UR-15-24040
Journal ID: ISSN 1948-7185
- Grant/Contract Number:
- 201308310077; 21201063; 20110074120020; FG02-05ER15667; AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 13; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; natural gas storage; direct gas adsorption calorimetry; thermodynamics; zero coverage enthalpy of adsorption
Citation Formats
Wu, Di, Guo, Xiaofeng, Sun, Hui, and Navrotsky, Alexandra. Thermodynamics of methane adsorption on copper HKUST-1 at low pressure. United States: N. p., 2015.
Web. doi:10.1021/acs.jpclett.5b00893.
Wu, Di, Guo, Xiaofeng, Sun, Hui, & Navrotsky, Alexandra. Thermodynamics of methane adsorption on copper HKUST-1 at low pressure. United States. https://doi.org/10.1021/acs.jpclett.5b00893
Wu, Di, Guo, Xiaofeng, Sun, Hui, and Navrotsky, Alexandra. Thu .
"Thermodynamics of methane adsorption on copper HKUST-1 at low pressure". United States. https://doi.org/10.1021/acs.jpclett.5b00893. https://www.osti.gov/servlets/purl/1221609.
@article{osti_1221609,
title = {Thermodynamics of methane adsorption on copper HKUST-1 at low pressure},
author = {Wu, Di and Guo, Xiaofeng and Sun, Hui and Navrotsky, Alexandra},
abstractNote = {Metal–organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH₄ adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH₄–CH₄ intermolecular interactions are minimized and the energetics solely reflects the CH₄–MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH₄ independent of coverage. The calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH₄ adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH₄–HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site.},
doi = {10.1021/acs.jpclett.5b00893},
journal = {Journal of Physical Chemistry Letters},
number = 13,
volume = 6,
place = {United States},
year = {Thu Jun 11 00:00:00 EDT 2015},
month = {Thu Jun 11 00:00:00 EDT 2015}
}
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